Caricides certain phosphorus containing amidine compounds as insecticides and a

ABSTRACT

Compounds of the formula:   IN WHICH R is lower alkyl or lower alkoxy; R1 is lower alkoxy or lower alkylthio; R2 is hydrogen, lower alkyl, phenyl, mono or disubstituted phenyl; and X is oxygen when R1 is lower alkylthio and sulfur when R1 is lower alkoxy as insecticides and acaricides, and a process for preparing the compounds above having X be oxygen.

United States Patent [1 1 Pallos Sept. 11, 1973 1 CERTAIN PHOSPIIORUS CONTAINING AMIDINE COMPOUNDS AS INSECTICIDES AND ACARICIDES [75] Inventor: Ferenc M. Pallos, Pleasant Hill,

Calif.

[73] Assignee: Stauifer Chemical Company, New

York, NY.

[22] Filed: Jan. 11, 1971 [21] Appl. No.: 105,688

Related U.S. Application Data [62] Division of Ser. No. 885,263, Dec. 15, 1969.

[52] U.S. Cl. 424/211, 424/DIG. 8 [51] Int. Cl A01n 9/36 [58] Field of Search 424/211, DIG. 8;

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 151,685 11/1962 U.S.S.R.

Primary Examiner-Albert T. Meyers Assistant ExaminerVincent D. Turner Attorney-Block, Baker & Adamcik [57] ABSTRACT Compounds of the formula:

9 Claims, No Drawings 1 CERTAIN PHOSPHORUS CONTAINING AMIDINE COMPOUNDS AS INSECTICIDES AND ACARICIDES This application is a divisional of copending applicas tion Ser. No. 885,263, filed Dec. 15, 1.969.

This invention relates to the use of certain novel phosphorus containing amidine compounds as insecticides and acaricides and ma process for preparinggthe phosphorus containing amidines.

The compounds of the present invention that are useful as insecticides and acaricides are those having the formula:

It x

\I -N=G-NH: R it:

in which R is lower alkyl having 1 to 4 carbon atoms, preferably l to 2 carbon atoms, or. lower alkoxy having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms; R is lower alkoxy having 1 to4carbon atoms, preferably l to 2 carbon atoms, or lower alkylthio'having l. to 4 carbon atoms, preferably l. to 2' carbon: atoms; R is hydrogen, lower alkyl having 1 to=6 carbonzatoms, preferably l to 3 carbon atoms; phenyl; mono or disubstituted phenyl in which the substituentsare lower alkyl having I to 4 carbon atoms, halogenor nitro; and X is oxygenwhen R is lower alkylthio and: sulfur when: R'is lower alkoxy.

Representative compounds are as-follows:

O, O-dimethyl thionophosphoryl butyramidine O, O-dibutyl thionophosphoryl butyramidine O, S-dimethyl phosphorylbutyramidine,

O, S-dibutyl phosphoryl butyramidine O-methyl, methyl-thionophosphonyl butyramidine O-butyl, butyl thionophosphonyl butyramidine O-methyl, methyl phosphonyl butyramidine O-butyl, butyl phosphonyl butyramidine O-methyl, O-butylthionophosphoryl butyramidine O-butyl, S-methyl phosphorylbutyramidine O-methyl, butyl thionophosphonyl butyramidine O-butyl, methyl phosphonyl butyramidine O,S-dimethyl phosphoryl form'amidine O,S-dimethyl phosphoryl acetamidine O,S-dimethyl phosphoryl heptamidine O,S-dimethyl phosphoryl benzaminde O,S-dimethyl phosphoryl chlorbenzamidine O,S-dimethyl phosphoryl methylbenzamidine O,S-dimethyl phosphoryl nitrobenzamidine Compounds having the formula: I

i --N: CNlh m-o a C is in which R, R, and R are as stated.

Preferably about 2 moles sodium hydroxide or other suitable acidacceptor is added with heavy stirring to an aqueous solution of equal mole amounts of the reactants. The reaction is exothermic and heating is not normally necessary, but'can be used. After the reaction is complete the reaction product, normally an oil, can

be recovered by conventional extraction techniques.

The process of: this invention for preparing compounds of theformula:

in which R is lower alkyl having 1 to 4 carbon atoms, preferably 1 to 2. carbon atoms, or. lower'alkoxy having 1 to- 4 carbon atoms, preferably 1 to 2 carbon. atoms; Ris hydrogen, lower alkyl,\having l to-6carbon atoms, preferably 1 to -3 carbon atoms; phenyl, mono or disubstituted phenyl: inwhich the substituents are lower alkyl having i to4 carbon atoms,halogen or nitro; and Ris lower alkyl having 1 m4 carbon atoms by reacting acompound of the formula:

in which R and R are as defined and R is lower alkyl having'l to 4 carboniatoms withacompoundof the f ormula:

, Rl inwhichiR is as defined. The process of this invention can be depicted by'the following equation:

inwhichR, R, R, and R areas stated. No special. reaction conditions are necessary for the process ofthis invention. It proceeds at room temperature, however, heating to reflux accelerates the reaction; Preferably,asolvent is usedbutis not necessary.

The iodide reactant can be used asthe solvent if desired, if usedinilarge enough excess. Preferably, at least an equal mole'amount of theiodidereactant should be usedfor a complete reaction. I Preparation: ot the; compounds of this invention and the-process or this invention is'illustrated by-the followingexamples.

EXAMPLE r dimethylphosphoro chloridothioateis added and 16.0

gr. (0.4 mole) NaOH in 80 ml. H O is dropped in under heavy stirring. The reaction is slightly exothermic and the temperature goes up to 39C. Stirring is continued for one hour. The reaction product is extracted with ether four times, ether dried over MgSO filtered, and stripped. The reaction product is confirmed to be the above structure. Yield: 36.0 gr. colorless oil. N 1.5160

EXAMPLE ll O,S-dimethyl phosphoryl butyramidine Prepared in Example I Prepared In Example ll INSECTICIDAL EVALUATION TESTS The following insect species were used in evaluation tests for insecticidal activity:

1. Housefly(I-IF) Musca domestica (Linn.)

2. Milkweed Bug (MWB) Oncopeltus fasciatus (Dallas) 3. Lygus Bug (LB) Lygus hesperus (Knight) 4. Bean Aphid (BA) Aphis fabae (Scop.)

The Housefly (HF) was used in evaluation tests of selected compounds as insecticides by the following procedure. A Stock solution containing 100 pig/ml; of the toxicant in an appropriate solvent was prepared. Aliquots of this solution were combined with 1 milliliter of an acetone-peanut oil solution in a glass Petri dish and allowed to dry. The aliquots were there to achieve desired toxicant concentration ranging from 100 pig/per Petri dish to that at which 50 percent mortality was attained. The Petri dishes were placed in a circular cardboard cage, closed on the bottom with cellophane and covered on top with cloth netting. :Twenty-five female houseflies, three to five days old, were introduced into the cage and the percent mortality was recorded after 48 hours. The LD-SO values are expressed in terms of pg per 25 female flies. The result of this insecticidal evaluation tests are given in Table II undeHHF.

In the Milkweed Bug (MWB) test, two-week old nymphs of Milkweed Bug (MWB) were placed in separate circular cardboard cages sealed on one end with cellophane and covered by a cloth netting on the other. Aliquots of the toxicants, dissolved in an appropriate solvent, were diluted in water containing 0.002 percent of a wetting agent, Sponto 221 (a polyoxyether of alkylated phenols blended withorganic sulfonates). Test concentrations ranged from 0.1 percent downward to that at which 50 percent mortality was obtained. Each of the aqueous suspensions of the candidate compounds were sprayed onto the insect through the cloth netting by means of a hand-spray gun. Percent mortality in each case recorded after 72 hours, and theLD-SO values expressed as percent of toxicant in the aqueous spray was recorded. These values are reported under the column MWB in Table II.

The Lygus Bug (LB) Lygus hesperus was'testedsimilarly as the Milkweed Bug, except 10 to 25 insects were used per cage. The caged insects were sprayed with the candidate compounds at concentrations ranging from 0.05 percent downward to that at which 50 percent mortality was obtained. After 24 and 72 hours, counts were made to determine living and dead insects. The LD-SO (percent) values were calculatedsThese values are reported under the column LB in Tablev II.

The insect species Black Bean Aphid (BA) Aphis fabae.(Scop.) was also employed in the testfor in secticidal activity. Young nasturtium (Tropaeolum sp.) plants, approximately 2 to 3 inches tall, were used as the host plants for the bean aphid. The host plant was infested with approximately 50 75 of, the aphids. The

test chemical was dissolved in acetone, added to water which contained a small amount of Sponto 221, an.

emulsifying agent. The solution was applied as a spray to the infested plants. Concentrationsranged from 0.05 percent downward until an LD-SO value was achieved. These results are given in Table II under the column llBAil.

ACARICIDAL EVALUATION TEST The two-spotted mite (28M), Tetranychus urticae (Koch) was employed in tests for miticides. Young pinto bean plants or lima bean plants (Phaseolus sp.) in 5 Table [I under the columns The percentage of kill of each test species was determined by comparison with control plants placed in distilled water or untreated soil. The LD-50 values were calculated. These systemic test results are reported in BA-sys and ZSM-sys.

HF, MWB, LB, BA, BA-sys., PE, Sys., g. percent percent percent p.p.m. percent p.p.m.

Compound Number:

the primary leaf stage were used as the hOst plantsTThe young pinto bean plants were infested with about 100 mites of various ages. Dispersions of candidate materials were prepared by dissolving 0.1 gram in IQ ml. of a suitable solvent, usually acetone. Aliquots of the toxicant solutions were suspended in water containing- 0.002% v/v Sponto 221, a polyoxyethylene ether sorbitan monolaurate, an emulsifying agent, the amount of water being sufficient to give concentrations of active ingredient ranging from 0.05 percent to that at which 50 percent mortality was obtained. The test suspensions were then sprayed on the infested plants to the point of run off. After 7 days, mortalities of the postembryonic form was determined. The percentage of kill was determined by comparison with control plants which had not been sprayed with candidate compounds. The LD-50 value was calculated using wellknown procedures. These values are reported under the column 2SM.-PE" in Table II.

SYSTEMIC EVALUATION TEST ton plugs. Only the roots were immersed. The test solu'.

tions were prepared by dissolvingthe compounds to be tested in a suitable solvent, usually acetone, and then diluting with distilled water. The final acetone concentration never exceeded about 1 percent. The toxicants were initially tested at a concentration of 10 parts per million (p.p.m.). Immediately after the host plant was placed in the test solution, it was infested with the test species. Mortalities were determined after seven days. Young nasturtium plants were used as the host plants for the bean aphid. The host plants were transplanted into one pound of soil that had been treated with the candidate compound. Immediately after planting in the treated soil the plants were infested with the aphids. Concentrations of toxicant in the soil ranged from 10 p.p.m. per pound of soil downward until an LD-50 value was obtained. Mortality was recorded after 72 hours.

As those in the art are well aware, various techniques are available for incorporating the active component or toxicantin suitable pesticidal compositions. Thus, the pesticidal compositions can be conveniently prepared in the form of liquids or solids, the latter preferably as homogeneous free-flowing dusts commonly formulated by admixing the active component with finely divided solids or carriers asexemplified by talc, natural clays, diatomaceous earth, various flourssuch as walnut shell, wheat, soya bean, cottonseed and so forth.

Liquid compositions are also useful and normally comprise a dispersion of the toxicant in a liquid media, although it may be convenient to dissolve the toxicant directly in a solvent such as kerosene, fuel oil, xylene, alkylated naphthalenes or the like and use such organic solutions directly. However, the more commonprocedure is to employ dispersions of the toxicant in an aqueous medium and such compositions may be produced by forming a concentrated solution of the toxicant in a suitable organic solvent followed by dispersion in water, usually with the aid of surface active agents. The latter, which may be anionic, cationic or non-ionic types, are exemplified by sodium stearate, potassium oleate, and other alkaline metal soaps and detergents such as sodium lauryl sulfate, sodium naphthalene sulfonate, sodium alkyl naphthalane sulfonate, methyl cellulose, fatty alcohol ethers, polyglycol fatty acid esters and other polyoxethylene surface active agents. The

proportion of these agents commonly comprises 1-15 percent by weight of the pesticidal compositions although the proportion is not critical and may be varied to suit any particular situation.

It is claimed:

l. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the. formula 2. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula in which R is methoxy, R is methylthio and R is methyl. 7

3. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula in which R is methoxy, R is methoxy and R is methyl. 4. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula in which R is methoxy, R is methylthio, and R is npropyl.

5. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula in which R is ethyl, R is methylthio and R is methyl.

6. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula in which R is methoxy, R is methylthio and R is ethyl..

7. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula in which R is ethyl, R is methylthio and R is ethyl.

9. The method of controlling insects andacarids:

comprising applying to the habitatthereof an-insecticidally or acardically effective amount of a compound having the formula is methylthio and R is n-propyl.

in which R is ethyl, R 

2. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula
 3. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula
 4. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula
 5. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula
 6. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula
 7. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula
 8. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acaricidally effective amount of a compound having the formula
 9. The method of controlling insects and acarids comprising applying to the habitat thereof an insecticidally or acardically effective amount of a compound having the formula 